Heterocyclic siloxanes for use in biocidal coatings and materials

ABSTRACT

Heterocyclic and acyclic silane monomers and siloxane polymers, and their halogenated derivatives, are provided for the purpose of functionalizing surfaces or materials so as to render them biocidal upon exposure to oxidative halogen solutions. The biocidal function can be imparted either before or after bonding or adhesion to the surface or material. The biocidal surfaces and materials can then be used to inactivate pathogenic microorganisms such as bacteria, fungi, and yeasts, as well as virus particles, which can cause infectious diseases, and those microorganisms which cause noxious odors and unpleasant coloring such as mildew. Examples of surfaces and materials which can be rendered biocidal in this invention include, but are not limited to, cellulose, chitin, chitosan, synthetic fibers, glass, ceramics, plastics, rubber, cement grout, latex caulk, porcelain, acrylic films, vinyl, polyurethanes, silicon tubing, marble, metals, metal oxides, and silica.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.10/400,165, filed Mar. 24, 2003, which claims the benefit of U.S.Provisional Application No. 60/388,968, filed on Jun. 14, 2002, eachapplication of which is incorporated herein expressly by reference inits entirety.

STATEMENT OF GOVERNMENT LICENSE RIGHTS

The U.S. Government has a paid-up license in this invention and theright in limited circumstances to require the patent owner to licenseothers on reasonable terms as provided for by the terms of Grant No.F087637-01-C-6004, awarded by the United States Air Force.

FIELD OF THE INVENTION

The present invention relates to the synthesis and use of silane andsiloxane compounds for the purpose of constructing coatings andmaterials which can be rendered biocidal by exposure to halogensolutions either before or after curing the coating or material. Thebiocidal coatings and materials can then be used to inactivatepathogenic microorganisms such as bacteria, fungi, and yeasts, as wellas virus particles, that can cause infectious diseases, and thosemicroorganisms that cause noxious odors and unpleasant coloring such asmildew. The coatings are compatible with a wide variety of substratesincluding cellulose, chitin, chitosan, synthetic fibers, glass,ceramics, plastics, rubber, cement grout, latex caulk, porcelain,acrylic films, vinyl, polyurethanes, silicon tubing, marble, metals,metal oxides, and silica.

BACKGROUND OF THE INVENTION

Previous attempts to incorporate biocidal activity into materials andcoatings have primarily involved two methods: (1) physical mixing(blending) of biocides into the materials and coatings, and (2) chemicalbinding of biocidal functional groups to the polymers or copolymerscomprising the materials and coatings. Chemical binding should bepreferable for long-term biocidal activity if the bound biocidalfunctionality does not adversely affect the other desired propertiessuch as strength, appearance, and chemical resistance of the material orcoating. For example, a significant amount of work has been performedconcerning rendering sponges biocidally active. This involvesencapsulation of a variety of weak biocides into the porous structure ofthe sponge, either through physical blending or chemical bonding to thesurface. The sponges modified in this manner can exhibit biocidalactivity, but the contact times necessary for action are generally long,and some pathogens are not inactivated even at contact times of severalhours. Anti-fouling polyurethanes have been prepared by chemicalincorporation of tributyl tin as described in U.S. Pat. No. 5,194,504and quaternary ammonium salts (see, for example, J. Appl. Polym. Sci.50:663 (1993) and J. Appl. Polym. Sci. 50:671 (1993)). Coatingscontaining organo tin compounds are being discredited as threats to theenvironment, and poly-quats are weak biocides that are non-regenerable.Thus, there is a definite need for more effective biocidal coatings andmaterials.

A new class of biocidal monomers and polymers known as N-halamines,which could be useful in producing biocidal coatings, has recently beendeveloped. A non-toxic, non-irritating, and cost effective material,poly-1,3-dichloro-5-methyl-5-(4′-vinylphenyl)hydantoin, is aninexpensive derivative of polystyrene, that was first described in U.S.Pat. No. 5,490,983. Subsequent disclosures of its biocidal propertiesfor use in disinfecting applications for water filters have recentlyoccurred (see, for example, Ind. Eng. Chem. Res. 33:168 (1994); WaterRes. Bull. 32:793 (1996); Ind. Eng. Chem. Res. 34:4106 (1995); J.Virolog. Meth. 66:263 (1997); Trends in Polym. Sci. 4:364 (1996); WaterCond. & Pur. 39:96 (1997)). The polymer is effective against a broadspectrum of pathogens including Staphylococcus aureus, Pseudomonasaeruginosa, Escherichia coli, Candida albicans, Klebsiella terrigena,poliovirus, and rotavirus, among others, causing large log reductions incontact times of the order of a few seconds in water disinfectionapplications.

N-halamine functional groups such as hydantoins, oxazolidinones, andimidazolidinones have also been employed recently in producing biocidalcellulose (U.S. Pat. No. 5,882,357), biocidal films on surfaces (U.S.Pat. No. 5,902,818), biocidal Nylon (U.S. patent application Ser. No.09/615,184), and biocidal polyester (U.S. patent application Ser. No.09/866,535); these patents and patent applications are herein expresslyincorporated by reference in their entirety.

U.S. Pat. No. 4,412,078 to Berger describes alkyl and alkoxysilylpropylhydantoin derivatives. Also, silylpropylisocyanurates havebeen reported for use as adhesive sealants (U.S. Pat. No. 3,821,218.)Moreover, much work has been done concerning attaching quaternaryammonium functional groups which are weak, non-regenerable biocides tovarious silicon compounds which can then be bonded to surfaces to renderthem weakly biocidal (see, for example, U.S. Pat. Nos. 3,560,385;3,730,701; 3,794,736; 3,814,739; 3,860,709; 4,411,928; 4,282,366;4,504,541; 4,615,937; 4,692,374; 4,408,996; 4,414,268; and 5,954,869).The N-halamine derivatives of the invention represent a significantimprovement in biocidal efficacy over prior art in terms of both therequired contact times and increased spectrum of activity.

SUMMARY OF THE INVENTION

Compounds according to the present invention have the followingstructures:

For structures (1)-(8) above, R1, R2, and R3 are independently selectedfrom a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 estergroup, wherein at least one of R1, R2, or R3 group is a C1-C4 alkoxy,hydroxy, chloro, or C1-C4 ester group; m=0, 1, or 2; n=1, 2, or 3 forstructures (1), (3), (7), and (8); p=1, 2, or 3; m+n+p=4; and R isdefined below.

L is a linker group that attaches R to the Si moiety. L is a linkeralkylene, amine, or ether group, comprised of 1-13 carbons, 0-3 nitrogenor oxygen atoms, or L is a linker alkylene group of 1-13 carbons and acarbamate, thiocarbamate, or urea functional group.

R groups suitable for structures (1), (2), (5), (7), and (9) above aregroups (11)-(21).

Imide-Linked Hydantoin

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group; and wherein X is at least one of chlorine orbromine. X can be hydrogen if the compound is represented by structures(5), a siloxane or (9), a modified substrate.

Amide-Linked Hydantoin

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group; and wherein X is at least one of hydrogen,chlorine or bromine.

Representative compounds having group (11) or (12) are those wherein R1,R2, R3 are independently selected from a methyl, ethyl, phenyl, methoxy,ethoxy, or hydroxy group; wherein at least one of R1, R2, or R3 is amethoxy, ethoxy, or hydroxy group; and wherein R4 and R5 areindependently selected from a methyl, ethyl, hydroxymethyl or phenylgroup.

Representative compounds having group (11) or (12) are those wherein R1,R2, and R3 are a methoxy or ethoxy group; R4 and R5 are a methyl group,and L is a linker alkylene, amine, or ether group, comprised of 1-7carbons and 0-1 nitrogen or oxygen atoms, or L is a linker alkylenegroup, comprised of 1-7 carbons and a carbamate, thiocarbamate, or ureafunctional group.

Representative compounds having group (11) or (12) are those wherein R1,R2, R3 are a methoxy group; X is chlorine; and L is a linker alkylenecomprised of 3 carbons.

Representative compounds having group (11) or (12) are those wherein R1,R2, R3 are a methoxy group; X is bromine; and L is a linker alkylenecomprised of 3 carbons.

Representative compounds having group (11) or (12) are those wherein R1,R2, and R3 are an ethoxy group; X is chlorine; and L is a linkeralkylene comprised of 3 carbons.

Representative compounds having group (II) or (12) are those wherein R1,R2, and R3 are an ethoxy group; X is bromine; and L is a linker alkylenecomprised of 3 carbons.

Representative compounds having group (11) or (12) are those wherein R1,R2, and R3 are a methoxy group; X is chlorine; and L is a linker amineor ether group comprised of 4 carbons, and 1 nitrogen or oxygen atom.

Representative compounds having group (11) or (12) are those wherein R1,R2, and R3 are a methoxy group; X is bromine; and L is a linker amine orether group comprised of 4 carbons, and 1 nitrogen or oxygen atom.

Representative compounds having group (11) or (12) are those wherein R1,R2, and R3 are an ethoxy group; X is chlorine; and L is a linker amineor ether group comprised of 4 carbons, and 1 nitrogen or oxygen atom.

Representative compounds having group (11) or (12) are those wherein R1,R2, and R3 are an ethoxy group; X is bromine; and L is a linker amine orether group comprised of 4 carbons, and 1 nitrogen or oxygen atom.

Representative compounds having group (11) or (12) are those wherein R1,R2, and R3 are a methoxy group; X is chlorine; and L is a linkeralkylene group comprised of 4 carbons and a carbamate, thiocarbamate, orurea functional group.

Representative compounds having group (11) or (12) are those wherein R1,R2, and R3 are a methoxy group; X is bromine; and L is a linker alkylenegroup comprised of 4 carbons and a carbamate, thiocarbamate, or ureafunctional group.

Representative compounds having group (11) or (12) are those wherein R1,R2, and R3 are an ethoxy group; X is chlorine; and L is a linkeralkylene group comprised of 4 carbons and a carbamate, thiocarbamate, orurea functional group.

Representative compounds having group (11) or (12) are those wherein R1,R2, and R3 are an ethoxy group; X is bromine; and L is a linker alkylenegroup comprised of 4 carbons and a carbamate, thiocarbamate, or ureafunctional group.

Imidazolidinone

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group; and wherein X is at least one ofhydrogen, chlorine, or bromine.

Representative compounds having group (13), (14), or (15), are thosewherein R1, R2, and R3 are a methoxy, ethoxy, or hydroxy group; R4, R5,R6, and R7 are a methyl group; and L is a linker alkylene, amine, orether group, comprised of 1-4 carbons, and 0-1 nitrogen or oxygen atoms,or L is a linker alkylene group, comprised of 1-4 carbons, and acarbamate, thiocarbamate, or urea functional group.

Oxazolidinone

wherein R4 is at least one of a C1-C4 alkyl, aryl, or hydroxymethylgroup; and wherein X is at least one of hydrogen, chlorine, or bromine.

Representative compounds having group (16) are those wherein R1, R2, andR3 are a methoxy, ethoxy, or hydroxy group; R4 is a methyl, ethyl, orhydroxymethyl group; and L is a linker alkylene group, comprised of 1-3carbons, or L is a linker alkylene group, comprised of 1-3 carbons, anda carbamate, thiocarbamate, or urea functional group.

Glycoluril

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group; and wherein X is independently selected from atleast one of hydrogen, chlorine, bromine, or hydroxymethyl; and whereinat least one X is hydrogen, chlorine, or bromine.

Representative compounds having group (17) are those wherein R1, R2, andR3 are a methoxy, ethoxy, or hydroxy group; R4 and R5 are a methylgroup; and L is a linker alkylene, amine, or ether group, comprised of1-4 carbons and 0-1 nitrogen or oxygen atoms, or L is a linker alkylenegroup, comprised of 1-4 carbons, and a carbamate, thiocarbamate, or ureafunctional group.

Isocyanurate

wherein X is independently selected from at least one of hydrogen,chlorine, bromine, or hydroxymethyl; and wherein at least one X ishydrogen, chlorine, or bromine.

Representative compounds having group (18) or (19) are those wherein R1,R2, and R3 are a methoxy, ethoxy, or hydroxy group; and L is a linkeralkylene, amine, or ether group, comprised of 1-4 carbons and 0-1nitrogen or oxygen atoms, or L is a linker alkylene group, comprised of1-4 carbons, and a carbamate, thiocarbamate, or urea functional group.

Triazinedione

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group; and wherein X is independently selected from atleast one of hydrogen, chlorine, bromine, or hydroxymethyl; and whereinat least one X is hydrogen, chlorine, or bromine.

Representative compounds having group (20) are those wherein R1, R2, andR3 are a methoxy, ethoxy, or hydroxy group; R4 and R5 are a methylgroup; and L is a linker alkylene, amine, or ether group, comprised of1-4 carbons and 0-1 nitrogen or oxygen atoms, or L is a linker alkylenegroup, comprised of 1-4 carbons, and a carbamate, thiocarbamate, or ureafunctional group.

Piperidine

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group; and wherein X is chlorine orbromine when on structure (1) or (2), but X is hydrogen, chlorine, orbromine when on structures (5), (7), or (9).

Representative compounds having group (21) are those wherein R1, R2, andR3 are a methoxy, ethoxy, or hydroxy group; R4, R5, R6, and R7 are amethyl group; and L is a linker alkylene, amine, or ether group,comprised of 1-4 carbons and 0-1 nitrogen or oxygen atoms, or L is alinker alkylene group, comprised of 1-4 carbons, and a carbamate,thiocarbamate, or urea functional group.

R groups suitable for structures (3) (4) (6) (8) and (10) are an aminoalkylene or a polyamino alkylene group comprising at least one N-chloroor N-bromo group. A representative group for structures (3) (4) (6) (8)and (10) is an amino propyl group.

For groups (5) (6) (9) and (10), n, is the number of repeating units,not to be confused with n of structures (1) (3) (6) and (7) where, n, isthe number of R moieties on Si. The repeating number of units, n, isgreater than or equal to 2. However, n, can be as much as 500, orgreater.

A method for making a modified substrate, comprises applying a solutionof a compound of structure (1), and water, to a substrate; drying thesolution and curing the substrate at an elevated temperature to providea modified substrate, wherein R in structure (1) is a heterocyclicN-Halamine. The solution can further comprise an alcohol. Alternatively,the solution can be an alkaline solution.

A method for making a modified substrate, comprises applying a solutionof a compound of structure (1), and water, to a substrate; drying thesolution; and curing the substrate at an elevated temperature to providea modified substrate, wherein R in structure (1) is a heterocyclic aminefrom at least an amide-linked hydantoin, imidazolidinone, oxazolidinone,isocyanulate, glycoluril, and triazinedione.

A method for making a modified substrate, comprises applying a solutionof a silane having a pendant heterocyclic amine, and water, to asubstrate; drying the solution; curing the substrate at an elevatedtemperature; and halogenating the heterocyclic amine with an oxidativehalogen compound to provide a modified substrate.

A method for making a modified substrate, comprises applying a solutionof a compound of structure (3), and water, to a substrate; drying thesolution; and curing the substrate at an elevated temperature to providea modified substrate.

A method for making a modified substrate, comprises applying a solutionof a silane having a pendant aminoalkylene or polyamino alkylene group,and water, to a substrate; drying the solution; curing the substrate atan elevated temperature; and halogenating the amino group with anoxidative halogen compound to provide a modified substrate.

A method for making a modified substrate, comprises applying a solutionof a compound of structure (5), and water, to a substrate; drying thesolution; and curing the substrate at an elevated temperature to providea modified substrate, wherein R in the structure (5) is a heterocyclicN-halamine.

A method for making a modified substrate, comprises applying a solutionof a siloxane of structure (5), and water, to a substrate; drying thesolution; and curing the substrate at an elevated temperature to providea modified substrate, wherein R in the structure (5) is a heterocyclicamine from at least an amide-linked hydantoin, imidazolidinone,oxazolidinone, isocyanurate, glycoluril, triazinedione, and piperidine.

A method for making a modified substrate comprises applying a solutionof a siloxane having a pendant heterocyclic amine, and water, to asubstrate; drying the solution; curing the substrate at an elevatedtemperature; and halogenating the heterocyclic amine with an oxidativehalogen compound to provide a modified substrate.

A method for making a modified substrate, comprises applying a solutionof a siloxane of structure (6), and water, to a substrate; drying thesolution; and curing the surface at an elevated temperature to provide amodified substrate.

A method for making a modified substrate, comprises applying a solutionof a siloxane having a pendant amino alkylene or polyamino alkylenegroup, and water, to a substrate; drying the solution; curing thesubstrate at an elevated temperature; and halogenating the amino groupwith an oxidative halogen compound.

The present invention provides numerous advantages, including theability of rendering surfaces and materials biocidal when the compoundsof the invention are bound thereto, and the amine moiety has an N-chloroor an N-bromo group.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing aspects and many of the attendant advantages of thisinvention will become more readily appreciated by reference to thefollowing detailed description, when taken in conjunction with theaccompanying drawings, wherein:

The FIGURE is an illustration of one embodiment of a reaction mechanismfor modifying a substrate according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention may be understood more readily by reference to thefollowing detailed description of specific embodiments and the examplesincluded therein.

A silane or silane compound can be a monomer to produce polymers orsiloxanes. The silanes and siloxanes have heterocyclic and acyclic aminemoieties. The heterocyclic amine moieties are bound by a linker group.The heterocyclic and acyclic amine moieties can impart biocidalfunctionality when the moieties have an N-chloro or an N-bromo group.The silanes and siloxanes can be bound to substrates, and the substratesrendered biocidal. A siloxane compound can be an oligomer or polymer.

As used herein, “the modified substrate” refers to a surface or materialto which a silane or siloxane compound having the structure (1), (2),(3), (4), (5), or (6) has been attached through one or more of themoieties R₁, R₂, and R₃. If X in the amine group is Cl or Br orcombinations thereof, the surface or material will be biocidal; if X inthe amine group is H, the surface or material will not be biocidal, butthe surface or material can be rendered biocidal by exposing it to asource of oxidative chlorine or bromine. The substrates are representedby structures (7), (8), (9), and (10).

The unhalogenated silane compound of the invention can be synthesized byreacting a heterocyclic amine with a base in a solvent, such as ethanol,followed by reaction of the resulting alkali metal salt with ahaloalkylsilane in a solvent such as anhydrous dimethylformamide (DMF)such that the linker L constitutes an alkylene group.

Alternatively, an unhalogenated silane compound of the invention can beprepared by reacting a heterocyclic amine containing a hydroxymethylsubstituent with an aminoalkylsilane, a haloalkylsilane, anisocyanatoalkylsilane, an isothiocyanatoalkylsilane, or a silyl urea ina solvent such as anhydrous dimethylformamide such that the linker Lconstitutes an amine or an ether moiety, an alkylene carbamate, analkylene thiocarbamate, or an alkylene urea, respectively.Alternatively, the unhalogenated silane compound of the invention can bean alkyleneamino or alkylene-poly-amino silane itself to which noheterocyclic amine is attached. In general, the raw materials used inthe synthesis of the silane compounds of the invention are inexpensiveand available commercially from vendors such as Aldrich Chemical Company(Milwaukee, Wis.), Fisher Scientific (Pittsburgh, Pa.), Gelest Inc.(Tullytown, Pa.), Acros, Inc. (Pittsburgh, Pa.), and TCI America(Portland, Oreg.).

For group 11, for example, 5,5-dimethylhydantoin can first be reactedwith potassium hydroxide in ethanol, followed by reaction of thepotassium salt of the hydantoin with chloropropyltrimethoxysilane inanhydrous dimethylformamide to produce5,5-dimethyl-3-trimethoxysilylpropylhydantoin according to the method ofBerger in U.S. Pat. No. 4,412,078. All of the starting reagentsnecessary to make this monomer are available commercially.

For group 13, for example, 2,2,5,5-tetramethyl-1,3-imidazolidin-4-one,prepared according to U.S. Pat. No. 5,057,612, can be treated with themild base sodium carbonate to neutralize the hydrochloric acid producedupon reaction of chloropropyltrimethoxysilane at the amine position onthe imidazolidinone ring.

For group 14, the strong base, potassium hydroxide can be used to formthe potassium salt at the amide nitrogen of the imidazolidinone ring inxylene as a solvent as in U.S. Pat. No. 4,448,969, followed by reactionwith the chloropropyltrimethoxysilane.

For group 16, 4-ethyl-4-hydroxymethyloxazolidinone, prepared accordingto U.S. Pat. No. 5,902,818, can be reacted with sodium metal to producethe sodium salt at the oxygen bonded to the exocyclic methylene group,followed by a nucleophilic substitution reaction withchloropropyltrimethoxysilane.

For groups 15 and 17, each possessing amide nitrogens, representativescan be produced by reacting 4,4,5,5-tetramethyl-1,3-imidazolidin-2-one,prepared according to U.S. Pat. No. 4,681,948, and dimethylglycoluril,available commercially, respectively, with potassium hydroxide, followedby reaction with chloropropyltrimethoxysilane as for the group 14 case.

For groups 18, 19 and 20, possessing reactive imide nitrogen moieties,the unhalogenated silane compounds can be made, for example, in aprocedure analogous to that for the silylhydantoin in group 11 byreacting a sodium or potassium salt of the isocyanurate (availablecommercially) or a triazinedione (prepared in analogous manner to aderivative described in U.S. Pat. No. 5,490,983), respectively, withchloropropyltrimethoxysilane. In the case of the isocyanurate of group18, two equivalents of chloropropyltrimethoxysilane can be used to bondthe trimethoxysilylpropyl moiety to two of the nitrogens of the triazinering, leaving one nitrogen free for reaction with halogen.

For group 12, two equivalents of a strong base, such as sodium hydride,can be employed to produce the disodium salt of the hydantoin, followedby reaction with one equivalent of chloropropyltrimethoxysilane, toproduce a mixture of the compounds of groups 11 and 12.

For group 21, the general procedure described in U.S. Pat. No. 4,684,726can be followed to produce, for example,3-(2,2,6,6-tetramethylpiperidine-4-oxy)propyltriethoxysilane.

The silane compounds can be rendered biocidal by reacting thecorresponding unhalogenated silane compounds, dissolved in water, atambient temperature with free chlorine from such sources as gaseouschlorine, sodium hypochlorite bleach, calcium hypochlorite,chloroisocyanurates, and dichlorohydantoins. In the case of thedichlorohydantoins, the chlorine moiety on the imide nitrogen shouldtransfer to the more stable amide nitrogen, if available. Likewise, thebrominated silane compounds can be prepared by exposing them in aqueoussolution at ambient temperature to free bromine from such sources asmolecular bromine liquid, sodium bromide in the presence of an oxidizersuch as potassium peroxy monosulfate, and brominated hydantoins.Halogenation can also be effected in organic solvents employing freeradical halogenating agents such as t-butyl hypochlorite.

The unhalogenated or halogenated silane compounds can be bound orimmobilized to a surface or material through either covalent bonding oran adhesive interaction depending on the nature of the surface ormaterial to provide a surface modified with the unhalogenated orhalogenated silane compounds. This can be accomplished by exposing thesurface or material to a solution of the unhalogenated silane compoundat temperatures in the range of 0 to 300° C., more preferably 20 to 150°C., depending upon the nature of the surface or material. Immobilizationof the halogenated silane compounds can be accomplished by exposing thesurface or material to a solution of the compound at temperatures in therange of 0 to 60° C., more preferably, 20 to 40° C., depending upon thenature of the surface or material. The solvent for the silane compoundsshould contain at least 50% water to be used in the conversion of anyalkoxy groups (comprising the R₁, R₂, and R₃ groups in structure II) tohydroxyl groups so as to provide binding sites to the surface ormaterial. Organic solvents such as dimethylsulfoxide, tetrahydrofuran,dimethylformamide, alcohols, acetone, ethyl acetate, and methylenechloride can also be used in conjunction with water for the silanecompounds, although alcohols are less useful for the halogenated silanecompounds because they partially protonate the nitrogen of theheterocyclic ring or alkyleneamino group liberating halogen. Base canalso be added to the aqueous solutions to enhance the solubility of thesilane compounds. If water is the only solvent used, the pH should beadjusted to greater than 12. Other additives can be introduced to thesolutions of the silane compounds to enhance binding to the surface ormaterials, e.g., potassium thiocyanate for binding to cellulose. Thesolutions containing the silane compounds can be exposed to the surfacesor materials by soaking, spraying, spreading, and the like. Followingdrying of the solution on the surface, curing at some temperature (whichdepends upon the surface or material composition, e.g., 25° C. forpaper, 95° C. for cotton fibers and glass) for 15 to 30 minutes, shouldbe performed.

The unhalogenated or halogenated silane compounds can also bepolymerized to form siloxane compounds before attaching them to surfacesby exposing them to an acid such as hydrochloric acid in mixtures ofethanol and water, or water alone. The reaction is illustrated in theFIGURE. The heterocyclic moieties can be introduced before or after thepolymerization.

The surface or material can be rendered biocidal if the unhalogenatedsilane or siloxane compounds are immobilized on the surface by exposureto a source of oxidative halogen, such as an aqueous solution of sodiumhypochlorite bleach, calcium hypochlorite, chloroisocyanurates, anddichlorohydantoins; or an organic solution of t-butyl hypochlorite, forchlorination, or an aqueous solution of molecular bromine liquid, sodiumbromide in the presence of an oxidizer such as potassium peroxymonosulfate, and brominated hydantoins for bromination. For example, anaqueous solution of 10% CLOROX can be used for efficient chlorinationwhich can be accomplished at ambient temperature by spraying or soakingthe surface or material with same. After halogenation, the surface ormaterial should be allowed to dry in air at temperatures up to 40° C.(ambient temperature is preferable if time permits) and rinsed withwater. The modified surface or material will then exhibit biocidalproperties for various time periods dependent upon the composition ofthe surface or material, the use pattern (contact with organisms andhalogen demand), and the storage temperature. When the bound halogencontent becomes too low for efficient biocidal activity, the modifiedsurface or material can be recharged with halogen in the same manner asfor the original charging noted above.

An alternate embodiment of attaching the biocidal moieties to surfacesis to first bond a silane or a siloxane compound containing asubstituted nucleophilic alkyl functional group to the surface, andsecond, bonding the heterocyclic N-halamine or heterocyclic amine groupto the tethered silane or siloxane through a nucleophilic substitutionreaction. For example, aminopropyltriethoxysilane can be bonded to asurface, and then the amino functionality can be reacted with3-hydroxymethylhydantoin to produce an anchored hydantoin that can thenbe halogenated in situ as described above to render the surfacebiocidal. Alternatively, the tethered aminopropyltriethoxysilane couldbe directly halogenated in situ as described above to achieve a biocidalsurface. In general, the halogen will be stabilized to a greater extentwhen bonded to nitrogen on a heterocyclic moiety as opposed to anacyclic moiety.

The mechanism of action of the biocidal surfaces and materials producedas described herein is believed to be a result of surface contact of theorganism with chlorine bromine covalently bound to the heterocyclicfunctional groups on the bound silane. The chlorine or bromine atoms aretransferred to the cells of the microorganisms where they causeinactivation through a mechanism not completely understood, but probablyinvolving oxidation of essential groups contained within the enzymescomprising the organisms.

A marked advantage of the biocidal surfaces and materials of thisinvention over prior technology is that the surfaces and materials aremuch more effective biocidally against pathogenic microorganisms, suchas Staphylococcus aureus and Pseudomonas aeruginosa, encountered inmedical applications than are commercial biocides such as the quaternaryammonium salts. The biocidal surfaces and materials serve a dualfunction: (1) inactivation of disease-causing pathogens, and (2)inactivation of odor-causing microorganisms. For this reason, theinvention will have widespread use in medical settings such ashospitals, nursing facilities, and research laboratories. It should alsobe useful for biocidal applications in a variety of other industrialsettings, as well as in the home.

Representative surfaces and materials that can be made biocidal withthis invention include envelopes, surgical gowns and gloves, sheets,bandages, sponges, table and counter tops, glassware, as well asarticles made from plastic, synthetic fibers, wood, chitin, chitosan,cement grout, latex caulk, porcelain, acrylic films, vinyl,polyurethanes, silicon tubing, marble, and metals.

EXAMPLES Example 1 Preparation of a Representative Unhalogenated SilaneCompound

Two trialkoxysilylpropylhydantoin derivatives were prepared according toa procedure similar to that outlined in U.S. Pat. No. 4,412,078.

A one-liter, three-neck-round-bottom flask was fit with a condenser,dropping funnel, and thermometer. To the flask was added a mixture of500 mL of ethanol, 64.0 g (0.5 mol) of 5,5-dimethylhydantoin (Acros,Inc.), and 28.0 g (0.5 mol) of potassium hydroxide. The mixture washeated to the boiling point until the solution became clear. Then thesolid potassium salt of the 5,5-dimethylhydantoin was isolated byevaporation of the ethanol solvent and the water produced in thereaction under reduced pressure. This salt was dried under vacuum at 60°C. for four days to form the anhydrous potassium salt. The dry salt wasthen placed back in the one liter flask where it was mixed with 500 mLof anhydrous N,N-dimethylformamide (DMF), and the mixture was heated at60° C. until a clear solution formed. Then 120.4 g (0.5 mol) of3-chloropropyltriethoxysilane (Aldrich Chemical Company) were addeddropwise over a one-hour period with stirring at ambient temperature.The mixture was then heated at 95° C. for 4 hours, cooled, and thepotassium chloride produced in the reaction was removed by filtration.The DMF solvent was removed by distillation to produce 150.0 g of abrown, viscous oil identified as3-triethoxysilylpropyl-5,5-dimethylhydantoin, the yield being 90.3% oftheoretical. The product was further purified by distillation underreduced pressure (16 mm Hg, fraction collected 235-238° C.) forelemental and spectroscopic characterization. Anal. Calcd. forC₁₄H₂₈SiN₂O₅: C, 50.6; H, 8.4; N, 8.4. Found: C, 50.3; H, 8.4; N, 9.0.¹H NMR (CDCl₃) δ 0.61 (2H), 1.22 (9H), 1.43 (6H), 1.73 (2H), 3.48 (2H),3.82 (6H), 7.17 (1H). IR (KBr) 740, 813, 1081, 1104, 1713, 1774, 2879,2989, 3279, 3485 cm⁻¹. MS (CI/CH₄) m+1, 333.

A procedure analogous to that described above utilizing3-chloropropyltrimethoxysilane (Aldrich Chemical Company) provided3-trimethoxysilylpropyl-5,5-dimethylhydantoin as a brown oil (8 mm Hg,fraction collected 194-195° C.), the yield being 92.0% of theoretical.¹H NMR (CDCl₃) δ 0.62 (2H), 1.43 (6H), 1.71 (2H), 3.53 (11H), 7.07 (1H).IR (KBr) 740, 812, 1091, 1450, 1712, 1773, 2835, 2959, 3000-3400 cm⁻¹.

Example 2 Preparation and Biocidal Efficacy of a RepresentativeChlorinated Silane Compound

A portion (6.11 g, 0.021 mol) of 3-trimethoxysilylpropylhydantoin,prepared as described in Example 1, was dissolved in 30 mL of methylenechloride in a 125 mL Erlenmeyer flask. Then 2.30 g (0.021 mol) oftert-butyl hypochlorite, prepared according to the method of Mintz, etal. (Org. Syn. 1969, 49:9-12), were added at room temperature, and theflask was stoppered, and the mixture was allowed to stand at roomtemperature for 3 hours with all light excluded. Vacuum evaporation wasemployed to remove the tert-butyl alcohol produced in the reaction. Theproduct, 1-chloro-3-trimethoxysilylpropyl-5,5-dimethylhydantoin, wasproduced as a yellow oil in 89.7% yield. It was stored at 4° C. in theabsence of light until use. The total chlorine content was determined tobe 10.36% by iodometric/thiosulfate titration as compared to thetheoretically possible value of 10.94%. The ¹H NMR signal at δ 7.07 for3-trimethoxysilylpropylhydantoin vanished upon chlorination indicatingthe presence of chlorine at the 1 position of the hydantoin moiety.

A 100.8 mg/L solution of the chlorinated silane compound, prepared asdescribed above, containing 11.02 mg/L total chlorine content inchlorine-demand-free water at pH 7 was challenged with S. aureusbacteria (ATCC 6538) for contact times of 5, 10, 30, and 60 min atambient temperature. Following the contact with the bacteria, furtherdisinfectant action was quenched by adding 0.02 N sodium thiosulfate.Serial dilutions were then plated onto trypticase soy agar, and colonycounts were made after 48 hours of incubation at 37° C. No growth wasdetected on the plates indicating a complete inactivation (>4.9 logs) atall of the contact times. Thus the chlorinated silane compound isbiocidal under the conditions tested. Neither lower contact times, norlower concentrations, were evaluated.

Example 3 Preparation of Biocidal Paper

Small pieces of white and brown commercial office envelopes were cutinto small squares. A 2% aqueous alkaline solution (pH 3 from NaOHaddition) of 3-triethoxysilylpropyl-5,5-dimethylhydantoin, prepared asdescribed in Example 1, was sprayed from an atomizer bottle onto bothsides of the paper samples until they became saturated. Then the wetsamples were cured until dry at 60° C. for 15 minutes. The cured sampleswere then sprayed on both sides with 10% CLOROX bleach until saturated,allowed to stand at ambient temperature for 10 minutes, rinsed 5 timeswith 50 mL portions of chlorine-demand-free water, and dried at ambienttemperature. The samples were stored in a vacuum desiccator until usefor analytical and microbiological characterization.

An iodometric/thiosulfate titration procedure was used to determine thechlorine loadings on the squares of the two kinds of paper as a functionof time after chlorination. The data are shown in Table 1. TABLE 1STABILITY OF CHLORINE ON PAPER SAMPLES Time Since Sample TypeChlorination (d) % Cl Loading mg/cm² Cl Loading White 0 0.823 0.055White 14 0.82 0.049 White 21 0.79 0.047 White 28 0.79 0.0454 White 360.781 0.0448 Brown 0 0.51 0.0344 Brown 14 0.50 0.032 Brown 21 0.4990.034 Brown 28 0.488 0.033 Brown 36 0.464 0.032

From the data in Table 1, it can be concluded that the treated papersamples stabilized chlorine very well over a 36-day period.

Freshly chlorinated paper samples (white and brown) were also challengedwith S. aureus bacteria (ATCC 6538). Control samples consisted oftreated, but unchlorinated paper, and untreated, but chlorinated paper.The data are presented in Table 2. TABLE 2 INACTIVATION OF S. AUREUS BYPAPER SAMPLES 1 Min Log 5 Min Log 10 Min Log 30 Min Log Sample TypeReduction Reduction Reduction Reduction White Contr 0 0 0 0 White Cl 0.13.0 >5.4^(a)  >5.4 Brown Contr 0 0 0 0 Brown Cl 1.9 4.6 >5.3   >5.3^(a)The > indicates that no surviving colonies could be detected.

From the data in Table 2, it can be concluded that both kinds of treatedpaper were effective in killing the bacteria. An untreated control whichwas subjected to the same chlorination procedure produced a reduction ofabout 1 Log during a 1 hour contact, but it is clear that most of theinactivation of the bacteria by the chlorinated treated samples can beattributed to the bound chlorine on the hydantoin moiety.

Similar results have been obtained for commercial paper file folders.

Example 4 Preparation of Biocidal Cotton

Swatches of Style 400 Bleached 100% Cotton Print Cloth (Testfabrics,Inc.) were treated with 3-triethoxysilylpropyl-5,5-dimethylhydantoin,prepared as described in Example 1, in the following manner. A treatmentbath was prepared containing 5.0 g of3-triethoxysilylpropyl-5,5-dimethylhydantoin, 3.0 g of potassiumthiocyanate, 50 mL of ethanol, and 50 mL of water. After 1 hour ofequilibration of the bath mixture, the cotton swatches were soaked inthe bath for 10 min. After partially drying in air at ambienttemperature, the swatches were cured for 1 hour at 95° C. The swatcheswere then soaked in a 0.5% liquid detergent solution for 15 min, rinsedwith tap water, and allowed to dry in air at ambient temperature. It wasfound that this treatment produced an average percent weight gain of theswatches of 5.5±0.6%; for an identical treatment except with theomission of KSCN the average weight gain was 4.7±0.3%. The swatches werecharged with chlorine by soaking in a 10% CLOROX solution for 30 min atambient temperature, rinsed thoroughly with chlorine-demand-free wateruntil test strips showed less than 0.2 mg/L of free chlorine in the washwater, and then dried in air at ambient temperature. It was found thatthe average chlorine loading on the swatches was 0.61±0.14%; without theuse of KSCN the average chlorine loading was 0.49±0.07%. The swatcheswere stored in a vacuum desiccator until use.

For comparison purposes, a biocidal quaternary ammonium compound(dimethyloctadecyltrimethoxysilylpropylammonium chloride, AldrichChemical Company) was also used to treat cotton swatches in a bathsimilar to that described above (with and without KSCN). The averageweight % add on was 14.7%.

Treated cotton swatches were challenged with S. aureus (ATCC 6538) andEscherichia coli (ATCC 2666) at a concentration of between 10⁸ and 10⁹CFU/mL in pH 7 phosphate buffer solution using a modified version ofAATCC Method 100. The swatches were quenched with 0.02 N sodiumthiosulfate solution at contact times of 10, 30, 60, and 120 min. Serialdilutions of the solutions contacting the swatches were plated onnutrient agar, incubated for 48 hours at 37° C., and plate counts weremade to determine the presence of viable bacteria. It was found that allS. aureus colonies (>5.7 logs) were inactivated by the swatches treatedwith 3-triethoxysilylpropyl-5,5-dimethylhydantoin (with or without KSCNin the treatment bath) in the contact time interval 10-30 minutes;whereas, the swatches treated with the quaternary ammonium saltexperienced only a 1.8 log reduction at 30 minutes. The control sample(cotton soaked in 10% bleach, rinsed, and dried) gave only a 0.4 logreduction at 30 minutes. It was found that all E. coli (>5.9 logs) wereinactivated by the swatches treated with3-triethoxysilylpropyl-5,5-dimethylhydantoin (with or without KSCN inthe treatment bath) in the contact time interval 60-120 minutes;whereas, the swatches treated with the quaternary ammonium saltexperienced only a 2.5 log reduction in this contact time interval. Thecontrol sample (cotton soaked in 10% bleach, rinsed, and dried) gave a 0log reduction at 120 minutes.

It can be concluded that cotton cloth treated with3-triethoxysilylpropyl-5,5-dimethylhydantoin (with or without KSCN inthe treatment bath) is biocidal. Furthermore, the hydantoin derivativeis more effective than the biocidal quat, and it seems to be somewhatmore effective against the Gram positive bacterium S. aureus thanagainst the Gram negative bacterium E. coli.

Washing tests have demonstrated that the cotton cloth treated by the3-triethoxysilylpropyl-5,5-dimethylhydantoin retains about 34% of itsbound chlorine after 50 wash cycles. A 1% bleach solution can be usedfor chlorination if the time of contact is 30 minutes.

A stability test during dry storage was also conducted on cotton samplescoated with 3-triethoxysilylpropyl-5,5-dimethylhydantoin. One half ofthe samples were coated in a bath containing 8% of the3-triethoxysilylpropyl-5,5-dimethylhydantoin in 50% ethanol in watersolution. The other half were treated in the same manner except thatKSCN was added to the treatment bath as described above. Thechlorination conditions and analytical method of measuring chlorineloadings were the same as discussed above. The samples were stored inplastic bags at ambient temperature; the bags were not air-tight. Theaverage chlorine loading for the samples treated in the presence of KSCNdeclined from 0.776% to 0.680% over a period of 50 days. For the samplesnot treated in the presence of KSCN, the decline was from 0.620% to0.540% over the same 50 day period. It can be concluded that the coatedcotton samples were fairly stable to loss of chlorine in dry storage.

Finally, tensile strength tests were run on coated cotton fibers. It wasfound that the average decline in tensile strength upon coating thecotton fibers with 3-triethoxysilylpropyl-5,5-dimethylhydantoin wasabout 8.7%; chlorination caused a further loss of only 0.6%. In thiscase the measurements were made upon the day of chlorination. A furtherdecline in strength would be expected with time after chlorination andwith frequency of rechlorination, since bleaching is known to cause slowdegradation in cotton fibers.

Example 5 Preparation and Testing of a Representative Siloxane Compound

A polymeric form of 3-chloropropylsiloxane was prepared as follows. In a500 mL flask, 72.14 g (0.3 mol) of 3-chloropropyltriethoxysilane wasmixed with 100 mL of ethanol, and while stirring the mixture, 77.8 g ofconcentrated hydrochloric acid were added dropwise. The mixture was thenrefluxed for 5 hours followed by removal of water and ethanol to producea viscous oil. The oil was held at 80° C. under vacuum (about 30 mm Hg)for 15 hours. The polymer (41.0 g) was obtained in 99% yield per unitbased upon the structure proposed below.

An elemental analysis based upon the proposed structure yielded: Calcd.for C₃H₇SiO₂Cl: C, 26.00; H, 5.05; Cl, 25.63. Found: C, 28.67; H, 4.85;Cl, 26.56. ¹H NMR (d₆-DMSO) δ 0.76 (2H), 1.79 (2H), 3.33 (1H), 3.60(2H).

Then the potassium salt of 5,5-dimethylhydantoin was prepared by slowlyadding 14.98 g (0.267 mol) of potassium hydroxide to 34.21 g (0.267 mol)of 5,5-dimethylhydantoin in 100 mL of DMF with stirring in a 500 mLflask. The mixture was further stirred at ambient temperature for 30minutes. Then 37.0 g (0.267 mol per unit) of the polymer of3-chloropropylsiloxane in 100 mL of DMF were added to the mixture, whichwas held at 100° C. for 6 hours with stirring. The potassium chloridesalt produced and the DMF solvent were removed by filtration andevacuation, respectively, to give 59.2 g crude yield (96.4%) of viscousoil. The viscous oil was further held at 150° C. under vacuum (about 30mm Hg) for 8 hours. The polymer product was a white

solid at ambient temperature produced in high yield based upon thestructure proposed below.An elemental analysis based upon the proposed structure yielded: Calcd.for C₈H₁₄SiN₂O₄: C, 41.74; H, 6.09; N, 12.17; Cl, 0.00. Found: C, 41.69;H, 6.14; N, 12.03; Cl, <0.25. ¹H NMR (d₆-DMSO) δ 0.52 (2H), 1.26 (6H),1.52 (2H), 3.29-3.36 (3H), 8.16 (1H); IR (KBr) 774, 1122, 1281, 1352,1422, 1452, 1709, 1772, 2935, 2977, 3000-3600 cm⁻¹. The infrared bandsat 1709 and 1772 cm⁻¹ are indicative of the presence of the hydantoinring in the siloxane polymer.

The siloxane polymer described above was coated onto 100% cotton fabric.This was accomplished by soaking swatches of the material for about 2minutes at ambient temperature in a bath containing 5 g of thepolysiloxane, 70 mL of ethanol, and 40 mL of water. The swatches werecured at 130° C. in air for 20 minutes, then soaked in 1.5% liquiddetergent for 15 minutes at ambient temperature, and then rinsedthoroughly with water. After drying in air at 50° C. for 30 minutes, theswatches were then soaked in 5% CLOROX at ambient temperature for 45minutes, rinsed thoroughly with water, and dried in air at 50° C. for 30minutes to remove any free chlorine present. An iodometric/thiosulfatetitration indicated a chlorine loading on the cotton material of about0.42%.

A biocidal evaluation of representative cotton swatches using theprocedure outlined in Example 4 showed that the treated materialproduced a 1.7 log reduction of S. aureus bacteria within a contact timerange of 10-30 minutes, but a 7.6 log reduction (total inactivation)within the range of 30-60 minutes. Thus a longer contact time wasrequired for the chlorinated siloxane polymer coating than for thesilane monomer coating described in Example 4, but the chlorine loadingwas also lower by 14.3%, so this result was not unexpected. TABLE 3EFFECTS OF WASHING TESTS ON COTTON COATED SWATCHES Coating TypeChlorination Chlorination Average (Monomer, M) Before After WashingChlorine (Polymer, P) Washing Washing Cycles Loading % M No Yes 5 0.26 MNo Yes 10 0.15 M No Yes 50 0.03 P No Yes 5 0.21 P No Yes 10 0.18 P NoYes 50 0.05 M Yes No 5 0.42 M Yes No 10 0.41 M Yes No 50 0.10 P Yes No 50.25 P Yes No 10 0.20 P Yes No 50 0.13 M Yes Yes 5 0.394 M Yes Yes 100.388 M Yes Yes 50 0.133 P Yes Yes 5 0.263 P Yes Yes 10 0.247 P Yes Yes50 0.146

Finally, a wash test was performed on swatches of cotton containing themonomer 3-triethoxysilylpropyl-5,5-dimethylhydantoin coating and thepolysiloxane coating, each chlorinated and unchlorinated, for comparisonpurposes. Two treatment baths were prepared, one containing an 8%solution of 3-triethoxysilylpropyl-5,5-dimethylhydantoin in a 50%solution of ethanol in water, the other containing an 8% solution ofsiloxane polymer prepared as described above in a 66.7% solution ofethanol in water. Identical cotton swatches were soaked in the two bathsfor 2.5 minutes at ambient temperature, cured in air at 130° C. for 20minutes, soaked in 1.5% liquid detergent at ambient temperature for 15minutes, rinsed thoroughly with water, and dried in air at 50° C. for 30minutes. Then one-half of the swatches of each type were chlorinated bysoaking them in 5% CLOROX at ambient temperature for 45 minutes. Thesechlorinated samples were rinsed thoroughly with water and dried in airat 50° C. for 30 minutes to remove all occluded free chlorine.Iodometric/thiosulfate titrations were performed on representativesamples to determine initial chlorine loadings. The average chlorineloading for the silane monomer-coated samples was 0.61%; for thesiloxane polymer-coated samples, the average chlorine loading was 0.40%.Then all types of coated swatches were subjected to laundry washingcycles using AATCC Test Method 61 (Test 2A Procedure). Samples wereevaluated after 5, 10, and 50 washing cycles for retention of thecoatings. Those samples not chlorinated before washing were chlorinatedby the procedure described above in order to assess how much chlorinecould be loaded after variable numbers of washing cycles. Thosechlorinated before washing were divided into two groups with half beingassessed for chlorine loading without rechlorination, the other halfbeing rechlorinated and then assessed for chlorine loading. Threeobservations are clearly evident from the data in Table 3. First, boththe silane and the siloxane coatings are partially lost upon successivewashings. Second, prechlorination reduces the rate of loss, probably dueto increasing the hydrophobicity of the surface, thus reducing the rateof hydrolysis loss of the siloxane coatings. Third, the siloxanecoating, which is not chlorinated to as high a level as the silane oneupon initial chlorination, is lost at a slower rate than is the silanecoating. For all of the coatings, at least partial biocidal efficacywould be regenerated upon rechlorination after 50 washing cycles. Mostprobably, a low concentration of bleach added to washing cycles shouldmaintain biocidal activity of the cotton material for the lifetime ofthe material.

Example 6 Alternative Preparation and Testing of a RepresentativeSiloxane Compound

To a one-neck round-bottom flask were added 35 g of3-triethoxysilylpropyl-5,5-dimethylhydantoin, prepared as described inExample 1, 18 mL of ethanol, 36 mL of water, and 0.25 to 0.5 mL ofdilute hydrochloric acid (1:1 by volume) such that the final pH was inthe range 3.5 to 5.5. The mixture was refluxed with stirring for 5 hoursand then poured into an open beaker which was left in a vacuum oven at60° C. for 3 hours, then 100° C. for 3 hours, then at 130° C. for 2hours, and finally at 170° C. for 2 hours. The resulting glossy solidwas a polymeric form of 3-trihydroxysilylpropyl-5,5-dimethylhydantoin.The material was not characterized other than by its performance asnoted below.

The polymeric material prepared as described above was then used to coatthe surfaces of military tenting, wood, glass, aluminum, and cotton. Forthe military tenting material, 2 g of the polymer were dissolved in 40mL of ethanol to produce a 5% solution. Swatches of tenting material cutinto 3-cm×4-cm rectangles were soaked in the polymer solution for 2 to 3minutes and then dried at ambient temperature for 48 hours. Then thepolymer coating was chlorinated by soaking the swatches in 10% CLOROXfor 30 minutes at ambient temperature. Following rinsing and drying atambient temperature, the chlorine loading on the surface of each swatchwas determined using iodometric/thiosulfate titration. The loadingaveraged 4.2×10¹⁶ Cl atoms per cm² after initial chlorination. Some ofthe swatches were reduced in thiosulfate and recharged. The averagechlorine loading following the recharge was 5.3×10¹⁶ Cl atoms per cm².The swatches were not tested for biocidal efficacy, but in ourexperience, any surface containing a chlorine loading of at least 1×10¹⁶atoms per cm² will be biocidal.

The same polymeric material was then coated onto wood (Tulip Poplar). Inthis case a 2.8% solution of the polymer in ethanol was used. Blocks ofthe wood having dimensions 5 cm×3.8 cm×1.9 cm were coated with thepolymer solution using a cotton swab. The blocks were dried in air andthen cured at 120° C. for 1 hour. Then chlorination was performed bysoaking in 10% CLOROX for 30 minutes at ambient temperature. Followingthorough rinsing with water and drying in air, an iodometric/thiosulfatetitration indicated that the average chlorine loading was 1.57×10¹⁷ Clatoms per cm², which should give excellent biocidal efficacy. Analogoustreatment of glass (FISHER microscope slides) and aluminum (REYNOLDSHeavy Duty Foil) gave chlorine loadings averaging 1.32×10¹⁷ Cl atoms percm² and 1.15×10¹⁷ Cl atoms per cm², respectively.

Also, a solution containing 2.5 g of the polymer in 100 mL of ethanol(2.5%) was sloshed in a plastic (PET) bottle and then poured out. Thesolution was allowed to dry on the inside surface of the bottle, thencured for 1 hour at 65° C. Then the bottle was filled with 10% CLOROXfor 30 minutes at ambient temperature. Following thorough rinsing withwater and drying in air, a iodometric/thiosulfate titration indicatedthat the average chlorine loading was 5.3×10¹⁶ Cl atoms per cm².

Finally, 100% cotton fabric swatches were tested. In this case 10 mL ofthe refluxed solution of polymer (the solid was not isolated) were mixedwith 100 mL of a 50% ethanol/50% water solution in a beaker. The cottonswatches (7 g) were soaked in the solution for 3 minutes, then partiallydried in air at ambient temperature, and then cured at 150° C. for 30minutes. After soaking in 5% CLOROX for 20 minutes, the swatches wererinsed and dried at ambient temperature. The average chlorine loading ofseveral swatches was determined by iodometric/thiosulfate titration tobe 0.438% Cl. Then the other treated swatches were subjected to laundrywashing cycles using AATCC Test Method 61 (Test 2A Procedure) followedby analytical determination of chlorine loading as a function of thenumber of wash cycles. After 5, 10, and 50 wash cycles the chlorineloadings averaged 0.282%, 0.279%, and 0.165%, respectively. A loading ofeven 0.165% Cl should exhibit reasonable biocidal efficacy.

Example 7 Preparation of and Coating with a Representative SilaneCompound

The potassium salt of 2,2,5,5-tetramethylimidazolidin-4-one was preparedby refluxing a solution of 14.2 g (0.1 mol) of2,2,5,5-tetramethylimidazolidin-4-one in 130 mL of xylene until all ofthe solid was dissolved. Then a solution of 5.6 g (0.1 mol) of potassiumhydroxide in 6.46 mL of distilled, deionized water was added dropwiseover a period of about 15 minutes, and the mixture was refluxed for anadditional 2 hours until about 98% of the water produced in the reactionwas removed. The solvent was removed under vacuum leaving the whitesolid potassium salt of 2,2,5,5-tetramethylimidazolidin-4-one. Then 100mL of anhydrous DMF was added to the salt, and the mixture was heated to100° C. until all solid was dissolved. Then 24.1 g (0.1 mol) ofchloropropyltriethoxysilane were added dropwise to the mixture at 100°C. over a period of 45 minutes, and the mixture was held at 100° C. foran additional 12 hours. Then the mixture was filtered at ambienttemperature to remove the potassium chloride produced in the reaction,and the DMF solvent was removed under vacuum. The crude product,3-triethoxysilylpropyl-2,2,5,5-tetramethylimidazolidin-4-one (32.1 g;92.6% crude yield), was a light brown viscous liquid which was useddirectly without further purification.

The crude product above was then coated onto cotton fabric. Swatches ofcotton were soaked in a bath containing 8.0 g of the crude product, 45mL of ethanol, and 45 mL of water for about 2 minutes, and then dried atambient temperature in air. Then the swatches were cured at 100° C. for45 minutes, soaked in 1.5% liquid detergent at ambient temperature for15 minutes, rinsed thoroughly with water, and dried at 50° C.Chlorination was performed on the swatches using 5% CLOROX at ambienttemperature for 45 minutes. Then the swatches were rinsed thoroughlywith water and dried in air at 45° C. for 30 minutes.Iodometric/thiosulfate titration indicated an average chlorine loadingof 0.114% for the cotton swatches. Although the initial chlorine loadingof this coating on cotton is lower than that of the3-triethoxysilylpropyl-5,5-dimethylhydantoin coating discussed inExample 4, its stability over time of storage and during washing isexpected to be greater.

Example 8 Preparation of and Coating with a Representative SilaneCompound

To 100 mL of ethanol in a 250 mL flask were added 76.6 g (0.4 mol) ofdichloro-3-chloropropylmethylsilane (Gelest, Inc.) dropwise at ambienttemperature over a period of 30 minutes. The mixture was then refluxedwhile stirring for 2 hours, and the excess ethanol was removed. Thecrude product (chloropropyldiethoxymethylsilane), 81.6 g, was obtainedas a viscous oil in 96.9% yield. Then 33.2 g (0.2 mol) of the potassiumsalt of 5,5-dimethylhydantoin, prepared as described in Example 1, weremixed with 42.1 g (0.2 mol) of the chloropropyldiethoxymethylsilane in150 mL of anhydrous DMF in a 500 mL flask, and the reaction mixture washeld at 110° C. for 8 hours. The potassium chloride produced in thereaction was removed by filtration, and the DMF by vacuum distillation.The 3-diethoxymethylsilylpropyl-5,5-dimethylhydantoin product (56.47 g,93.5% yield) was then used without further purification to coat cottonswatches. The swatches were soaked in a 10% solution of the3-diethoxymethylsilylpropyl-5,5-dimethylhydantoin in 66.7% ethanol inwater for 2.5 minutes at ambient temperature and then cured in air at140° C. for 15 minutes. The treated swatches were then soaked in 1.5%liquid detergent at ambient temperature for 15 minutes, rinsedthoroughly with water, and dried in air at 50° C. for 30 minutes. Theswatches were then chlorinated by soaking in 5% CLOROX at ambienttemperature for 45 minutes, rinsed thoroughly with water, and dried inair at 50° C. to remove all occluded free chlorine. The chlorine loadingwas determined by iodometric/thiosulfate titration to be 0.733%. Thismagnitude of loading should give excellent biocidal performance.Furthermore, the increased hydrophobicity of the coating due toreplacement of one ethoxy (hydroxy) group by the methyl alkyl group mayrender the surface more resistant to removal during washing than for thecoating described in Example 5. Multi-washing cycles have not yet beenperformed for the coating described in this example.

Example 9 Preparation of and Coating with a Representative SilaneCompound Containing an Amine Functional Group in the Linker

To 11.06 g (0.05 mol) of 3-aminopropyltriethoxysilane in 75 mL ofethanol were added 9.52 g (0.05 mol) of3-(2′-chloroethyl)-5,5-dimethylhydantoin. The mixture was refluxed for 5hours, and then the ethanol solvent was removed under reduced pressureto give 18.10 g of a brown viscous oil (87.9% yield of3-[2′-(3′-triethoxysilylpropyl)aminoethyl]-5,5-dimethylhydantoinhydrochloride which was used without further purification.

A bath containing 5.0 g of the crude product described above in 100 mLof a 50% ethanol/water solution was prepared. Cotton swatches weresoaked in the bath for 30 minutes. The swatches were then cured at 95°C. for 1 hour, followed by soaking in 1.5% liquid detergent for 15minutes, and rinsing thoroughly with water. After drying at 50° C., theswatches were chlorinated with a 5% solution of CLOROX for 5 minutes atambient temperature. Following a thorough rinse with water, the swatcheswere held at 50° C. in air until dry and then further dried in airovernight at ambient temperature. The chlorine loading was determined tobe 0.44% by iodometric/thiosulfate titration.

The crude product from above was also used to treat sand. Sand (OttawaSand Standard, 20-30 mesh, Fisher Chemicals) was stirred in a bathcontaining 5% of the crude product and 100 mL of a 50% ethanol/watersolution for 30 minutes at ambient temperature. The treated sand wascollected by filtration, cured at 95° C. in air for 1 hour, soaked inmethanol for 10 minutes, rinsed with water, and then dried at 45° C. inair for 2 hours. The sand was then chlorinated by exposure to 50% CLOROXsolution for 15 minutes. After thorough rinsing with water and drying at50° C. in air for 2 hours, the chlorine loading was found to be 0.11% byiodometric/thiosulfate titration.

Example 10 Odor Control Properties of Non-Woven Matrix Coated with aRepresentative Chlorinated Silane Compound

3-triethoxysilylpropyl-5,5-dimethylhydantoin, prepared as described inExample 1, was used to treat non-woven pads consisting of 1 gram of awood pulp matrix such as is used in diapers and incontinence products. A5% solution prepared in a distilled water and ethanol 1:1 mixture wasapplied to pads of the wood pulp fibers, and they were then left to soakfor 5 minutes. Excess solution was vacuum suctioned from the pads, whichwere then dried in an oven at 90° C. for two hours. Untreated pads werealso subjected to exposure to water and ethanol as controls, and weresimilarly dried.

Dried coated test samples and uncoated control pads were then treated byexposure to 10% sodium hypochlorite solution for 15 minutes, after whichthey were rinsed exhaustively with distilled water, and then vacuumdried to remove any unbound, free chlorine. Additional control padsconsisted of wood pulp coated with3-triethoxysilylpropyl-5,5-dimethylhydantoin but not exposed to thehypochlorite bleach charge. These were rinsed thoroughly along with thetest articles, and dried under the same conditions. All dried pads werethen left for 48 hours on the bench of a laboratory fume hood beforebeing used in the experiments.

All test and control pads were then exposed to an inoculum designed togenerate ammonia odor as a result of bacterial action on urine,simulating events in an infant or adult human diaper. Each inoculumconsisted of 1 mL of pooled human female urine, supplemented with 50 mgof urea, mixed with 0.1 mL of a culture of Proteus mirabilis bacteria,and spread evenly over the surface of the pad. All pads were then keptat 37° C. for six hours in individual containers sealed with parafilm.At the end of this period the samples were removed from the incubator,and the amount of ammonia gas in the head space above each pad wasmeasured as an indicator of the degree of odor generated in the urine.Ammonia measurements were made using a Drager gas sampling device.

All control samples at the end of the incubation showed more than 30 ppmof ammonia present in the head space above the pads. In the case of thepads coated with 3-triethoxysilylpropyl-5,5-dimethylhydantoin andhalogenated with chlorine, the samples showed no detectable ammonia(lower limit of detection, 0.25 ppm). Control samples had a powerfulodor of ammonia, readily detected by the human nose, whereas the samplesabove the treated test pads had no detectable odor whatsoever.

The results in this example show that halogenated3-triethoxysilylpropyl-5,5-dimethylhydantoin can coat wood pulp fibers,and that this coating is highly effective in inhibiting microbialproduction of odor by suspensions of bacteria in human urine. Moreover,once applied to the fibers, this antimicrobial coating is not readilyremoved by extensive washing, and subsequent drying. Coated non-wovenmatrices of wood pulp (cellulose) and other fibers should be excellentas components of diapers and incontinence pad devices which will resistthe development of odors during normal use.

Example 11 Antiviral Properties of Surfaces Coated with Representative aChlorinated Silane Compound

Soft and hard surfaces were treated by exposure to a solution of3-triethoxysilylpropyl-5,5-dimethylhydantoin, as prepared in Example 1,and then halogenated with hypochlorite bleach, prior to being exposed toa challenge inoculum of a virus (MS2 phage). After passage of measuredcontact times, recovery of viable infective virus particles wasattempted from treated and control surfaces in order to demonstrate theinactivating efficacy of the halogenated surfaces. Soft surfaces used inthese experiments were swatches of woven cotton textiles, and slabs cutfrom a standard kitchen sponge. Hard surfaces used were porcelain andmarble tiles.

For the preparation of antimicrobial textiles, fabric and sponge sampleswere immersed in 5% solution of3-triethoxysilylpropyl-5,5-dimethylhydantoin and dried in a convectionoven at 90° C. for two hours. Chlorination of the coated cellulosematerials was accomplished by placing them in the wash chamber of astandard, household washing machine, and processing them through anormal, cold water small load cycle, with one rinse. The washingsolution contained 100 mL of CLOROX ULTRA (sodium hypochlorite) perload. This procedure was used to simulate an everyday process that couldbe used by the consumer to charge coated fibers of treated textiles in ahome environment. Drying of each load was done in a domestic dryer for30 minutes at medium heat setting. Successful chlorination of launderedtextiles was confirmed by iodometric/thiosulfate titration of the boundchlorine on swatches of each test material. Uncoated, normal fabric wasused as a control in these experiments. Chlorine contents werecalculated and expressed as ppm Cl⁺. These values for cotton wereapproximately 4000, and for the sponge slabs 1000-2000 ppm,

Hard surface samples were exposed to the3-triethoxysilylpropyl-5,5-dimethylhydantoin by using a sponge soaked inthe 5% solution, before transfer to a drying oven at 90° C. for twohours. Alternatively, test tiles were immersed in the 5% solution,before drying. Chlorination of hard surfaces was accomplished bysponging on a 10% solution of CLOROX bleach and allowing the samples tostand for up to 20 minutes at room temperature before rinsingexhaustively with distilled water, and allowing them to dry at roomtemperature. Uncoated tiles were used as controls; they were exposed tohypochlorite before rinsing and drying. In addition, coated surfacesthat remained uncharged with chlorine were used as controls in challengeinocula experiments. Chlorine bound to hard surfaces was determined byiodometric/thiosulfate titration, and chlorine contents were expressedas μg Cl⁺ per square cm. These values were 3.3 for the porcelain, and6.9 for the marble tile.

Challenge inocula for determination of antiviral activity of halogenatedcoatings were made with suspensions of MS2 virus harvested from lawns ofEscherichia coli bacterial host cells on trypticase soy agar (TSA)plates using standard methods. The test protocol used was a slightlymodified version of Method 100-1998 from the American Association ofTextile Chemists and Colorists (AATCC). One mL aliquots of a stocksuspension of virus of known titer were applied to swatches of thetextiles, 5 cm in diameter, for defined contact times (ct) at roomtemperature. The swatches were then treated with 0.02 M sodiumthiosulphate solution to neutralize any remaining active chlorine, andagitated in phosphate buffered water for recovery of infective virusparticles. Enumeration of recovered organisms was accomplished byplating dilutions of the recovery solution onto E. coli lawns on TSA.Each infective virus particle recovered in this assay gives rise to aplaque of lysed host cells after 24 hours of incubation at 37° C. Byenumeration of visible plaques on the surface of the agar plates, theproportion of the challenge inocula remaining after contact with theswatches was determined. The results are expressed as Log 10 reductionsin the test samples when compared to the recovery from untreated controlswatches.

Inoculation of hard surfaces was done using a protocol which was similarin principle. It was modified to allow for the retention of thechallenge inocula in contact with the hard test surface during theentire incubation period. This was accomplished by creating a “sandwich”of the inoculum suspension between a glass microscope cover slip and thetest article. By this means, losses of the inocula by evaporation wereavoided, and the exact surface area in contact with the challengeorganisms was readily calculated. Recovery of infective virus particleswas again achieved by agitation in recovery solution containingthiosulphate neutralizer, and the results again expressed as reductionsin Log 10 titer of the MS2 virus compared to the controls.

Results showed that cellulose textile and sponge samples coated withchlorinated 3-triethoxysilylpropyl-5,5-dimethylhydantoin showed aremarkable capacity to inactivate the tough viral particles of MS2phage. Reductions of approximately 4 logs were consistently achievedwith cellulose substrates after 24 hours of contact. On hard surfacestiters were reduced by approximately 2 logs after contact times of aslittle as 6 hours. Small non-enveloped viral particles are particularlydurable in the environment and generally not highly susceptible tochemical deactivation. These data therefore indicate that antimicrobialsurfaces created with halogenated3-triethoxysilylpropyl-5,5-dimethylhydantoin will have demonstrableantiviral functions when used as a means of protecting environmentalsurfaces against persistent contamination by viruses.

Example 12 Antifungal Properties of Surfaces Coated with aRepresentative Chlorinated Silane Compound

Soft and hard surfaces were treated by exposure to a solution of3-triethoxysilylpropyl-5,5-dimethylhydantoin, prepared as described inExample 1. The soft surfaces used for detection of antifungal propertieswere woven textiles composed of fibers of polypropylene, cotton(cellulose), polyester, rayon, and slabs from a cellulose kitchensponge. Hard surfaces prepared were polyvinylchloride (PVC) sheets, andporcelain and marble tiles. Challenge inocula of prepared surfacesconsisted of aliquots of stock suspensions of spores of Aspergillusniger (ATCC # 1004), a black mold, harvested from cultured lawns onPotato Dextrose Agar (PDA) plates. Methods for preparation of thehalogen charged surfaces and protocols for challenge were as describedin Example 11. In this case recovery of Aspergillus was accomplished bythe plate dilution method on PDA, and the results were expressed as log10 reductions compared to the controls. Contact times varied from 24-72hours, considerably longer than was allowed for other organisms becauseof the well established durability of black mold spores under a widerange of physical and chemical conditions.

Chlorine concentrations on the tested soft surfaces ranged fromapproximately 800 on the synthetic fibers up to 4000 ppm on rayonfabrics. Hard surfaces were shown to range from 4.1 μg per cm² for thePVC, up to 6.9 μg per cm² for the marble tiles. All of the soft and hardsurfaces tested showed activity against Aspergillus black mold. Aftercontact times of 24 hours on cotton, reductions of 8 logs were observedin mold concentrations, with a 4 log reduction recorded for the spongeslabs. On synthetic fibers reductions of 5 logs (polypropylene,polyester) were observed after 72 hours of contact. On hard surfaces thecorresponding log reductions at 72 hours after spore inoculation were 4(marble), 5 (porcelain), and 4 (vinyl).

These data indicate that effective control of spores of molds can beexpected from the use of halogenated coatings of3-triethoxysilylpropyl-5,5-dimethylhydantoin on a variety of soft andhard substrates. It is likely that the disadvantages of odor and blackdiscoloration associated with mold growth can be avoided by use of thesecoatings, and their periodic recharge by exposure to free halogen inbleach.

Example 13 Anti-Yeast Properties of Surfaces Coated with aRepresentative Halogenated Silane

Soft and hard surfaces were treated by exposure to solutions of3-triethoxysilylpropyl-5,5-dimethylhydantoin prepared as described inExample 1. Challenge inocula for determination of activity directedagainst yeasts consisted of suspensions of Candida albicans (ATCC #102301) harvested from PDA plates. Procedures for preparation of halogencharged surfaces, plates, and the exposure of test articles were asdescribed in Example 11. Recovery of viable Candida was accomplished bythe plate dilution method on PDA.

All halogen charged surfaces expressed activity against inocula of yeastorganisms in this test. Reductions in viable yeasts in plate counts wererapid on cotton surfaces (5 logs in two hours of contact), but tooklonger on synthetic textiles (4 logs in 24 hours on polyester). On hardsurfaces reductions of up to 4 logs took place in 6 hours of contact.

These results indicate that antimicrobial coatings consisting ofhalogenated 3-triethoxysilylpropyl-5,5-dimethylhydantoin can be expectedto exert powerful anti-yeast activities on soft and hard surfaces.Yeasts, such as Candida, are known to cause dermal irritation indiapers, to cause severe odors, and to colonize and persist on manysurfaces in biofilm slime layers. Products containing these compoundsmay therefore be useful in reducing the clinical and nuisancesignificance of yeast microbes.

Example 14 Anti Bacillus (Bacterial) Spore Activity of Surfaces Coatedwith a Representative Halogenated Silane Compound

Soft and hard surfaces were treated by exposure to solutions of3-triethoxysilylpropyl-5,5-dimethylhydantoin, prepared as described inExample 1, and charged with chlorine as described in Example 11.Challenge inocula for the detection of activity versus bacterial sporeswere prepared from suspensions of spores of Bacillus subtilis. Recoveryof viable organisms from challenged surfaces was done on TSA plates, andenumeration was accomplished by the plate dilution method.

The most significant reductions in viable B. subtilis spore counts ontextile substrates were obtained after prolonged exposures on cotton andon polyester (>2 logs in 96 hours), while spores in contact withcellulose sponge were depleted by >5 logs in the same contact period. Onhard surfaces reductions up to 4 logs were seen on marble, vinyl, andporcelain when contact times were extended to 96 hours.

These results indicate that chlorine-charged antimicrobial surfacesprepared with 3-triethoxysilylpropyl-5,5-dimethylhydantoin coatings areeffective even on the most resistant stages of bacteria, the spores ofanaerobic organisms, provided sufficiently long contact is allowed. Thismay be useful in the killing of spores trapped in non-woven matrix airfilters, for example, or in the matrix used for filtration of otherprotective devices, in air duct surfaces, and in other situations whereoccupational exposure of workers to such organisms is a hazard, or inthe circumstances where deliberate distribution of such spores may beintroduced in acts of biological warfare or bioterrorism.

Example 15 Chlorine Binding by a Representative Silane Compound on Hardand Soft Surfaces

A variety of surfaces were coated with the3-triethoxysilylpropyl-5,5-dimethylhydantoin monomer, prepared asdescribed in Example 1, then cured at various temperatures, andchlorinated with dilute solutions of CLOROX using similar procedures tothose discussed in previous examples. The surfaces were then evaluatedfor their efficacies in loading chlorine either quantitatively byiodometric/thiosulfate titration or qualitatively by colorimetricvisualization of exposure of the surfaces to potassium iodide and starchsolution. The soft materials bound chlorine in the range of 500 to 5000ppm expressed as Cl⁺, while the hard surfaces bound it in the range of5.8×10¹⁶ to 2.5×10¹⁷ Cl atoms per cm².

The following materials showed efficacy in chlorine binding in thestudy: glass, sand, ceramics, nylon, acrylonitrile, latex rubber,polyvinylchloride laminates, polyester, polyurethane, TYVEK, silica gel,chitosan, chitin, Formica, unglazed porcelain, glazed porcelain,aluminum, silicon tubing, clear acrylic films, steel, cement grout, andlatex caulk. In fact, no material tested failed to bind chlorine aftertreatment.

This example demonstrates a great versatility of chlorine binding tosurfaces treated with the 3-triethoxysilylpropyl-5,5-dimethylhydantoinmonomer. The other silane monomers and siloxane polymers which are thesubjects of this invention should behave in similar fashion, and if aloading of at least 1×10¹⁶ atoms of Cl per cm² can be obtained, thesurfaces will then exhibit biocidal activity.

Example 16 Antimicrobial Activity of Textile Surfaces Coated with aRepresentative Acyclic Silane Compound

Cotton textiles were coated with 3-aminopropyltriethoxysilane byexposure to aqueous solutions of 5% of this compound, followed by curingthe woven fabric at 100° C. for 60 minutes in air, or by use of ahousehold dryer on high setting for 30 minutes. Swatches of the treatedfabric were charged with chlorine, and then challenged with suspensionsof Staphylococcus aureus; enumeration of recovery was accomplished usingthe methods described in Example 11. Chlorine contents of chargedoven-cured textiles ranged up to 5000 ppm (5 mg per g of material)immediately after drying, but diminished to 2300 ppm in approximately 14days at 20° C. Chlorine concentrations in dryer-prepared swatches werenever higher than 2500 ppm, even when fresh. Reductions of viableorganisms in freshly chlorinated oven-dried swatches were in excess of 4logs, after as little as 15 minutes of contact. Longer contact times (30minutes) were required to reach this level of efficacy in dryer-curedtextiles.

These results indicate that acyclic siloxanes can bind to cellulosetextiles, and when charged with chlorine, can exhibit potentantimicrobial effects, but with less durability than with the cyclicN-halamine series. As a general rule, N—Cl or N—Br bonds are alwaysstronger when in cyclic molecules than they are in their acyclicanalogs. Nevertheless, these properties may find utility in thepreparation of biocidal textiles that are subject to frequent rechargecycles such as clothing and certain cleaning tools, such as mops andcloths.

While the preferred embodiment of the invention has been illustrated anddescribed, it will be appreciated that various changes can be madetherein without departing from the spirit and scope of the invention.

1. A compound having the structure(R-L)_(n)-Si-(R₁)_(4-n) wherein R₁ is independently selected from aC1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group,wherein at least one R1 group is a C1-C4 alkoxy, hydroxy, chloro, orC1-C4 ester group; wherein L is a linker group; wherein n=1, 2, or 3;and wherein R is at least one of an amide-linked hydantoin,imidazolidinone, oxazolidinone, isocyanurate, glycoluril, ortriazinedione.
 2. The compound of claim 1, wherein L is a linkeralkylene, amine, or ether group, comprised of 1-13 carbons and 0-3nitrogen or oxygen atoms, or L is a linker alkylene group of 1-13carbons and a carbamate, thiocarbamate, or urea functional group.
 3. Thecompound of claim 1 having the structure

wherein R1, R2, and R3 are independently selected from a C1-C4 alkyl,aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, wherein atleast one of R1, R2, or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4ester group; wherein L is a linker group; and wherein R is at least oneof an amide-linked hydantoin, imidazolidinone, oxazolidinone,isocyanurate, glycoluril, or triazinedione.
 4. The compound of claim 3,wherein R has the structure

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group.
 5. The compound of claim 3, wherein R has thestructure

wherein R4, R5, R₆, and R₇ are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group.
 6. The compound of claim 3, whereinR has the structure

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group.
 7. The compound of claim 3, whereinR has the structure

wherein R4 at least one of a C1-C4 alkyl, aryl, or hydroxymethyl group.8. The compound of claim 3, wherein R has the structure

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group.
 9. The compound of claim 3, whereinR has the structure

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group; wherein X is independently selected fromhydrogen or hydroxymethyl, and wherein at least one X is hydrogen. 10.The compound of claim 3, wherein R has the structure

wherein X is independently selected from hydrogen or hydroxymethyl, andwherein at least one X is hydrogen.
 11. The compound of claim 3, whereinR has the structure

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group; wherein X is independently selected fromhydrogen or hydroxymethyl, and wherein at least one X is hydrogen.
 12. Asiloxane, comprising the structure

wherein, n≧2; R1 is at least one of a C1-C4 alkyl, aryl, C1-C4 alkoxy,hydroxy, chloro, or C₁-C₄ ester group; wherein L is a linker group; andwherein R is a heterocyclic amine.
 13. The siloxane of claim 12, whereinR is at least one of a hydantoin, imidazolidinone, oxazolidinone,isocyanurate, glycoluril, triazinedione, or piperidine.
 14. The siloxaneof claim 12, wherein R has the structure

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group.
 15. The siloxane of claim 12, wherein R has thestructure

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group.
 16. The siloxane of claim 12, wherein R has thestructure

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group.
 17. The siloxane of claim 12,wherein R has the structure

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group.
 18. The siloxane of claim 12,wherein R has the structure

wherein R4 is at least one of a C1-C4 alkyl, aryl, or hydroxymethylgroup.
 19. The siloxane of claim 12, wherein R has the structure

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group.
 20. The siloxane of claim 12,wherein R has the structure

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group; wherein X is independently selected fromhydrogen or hydroxymethyl, and wherein at least one X is hydrogen. 21.The siloxane of claim 12, wherein R has the structure

wherein X is independently selected from at least one of hydrogen orhydroxymethyl, and wherein at least one X is hydrogen.
 22. The siloxaneof claim 12, wherein R has the structure

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group; wherein X is independently selected from atleast one of hydrogen or hydroxymethyl, and wherein at least one X ishydrogen.
 23. The siloxane of claim 12, wherein R has the structure

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group.
 24. A modified substrate,comprising the structure(R-L)_(n)(R₁)_(m)-Si-(O)_(p)-wherein, m=0, 1, or 2; n=1, 2, or 3; p=1,2,or 3; and m+n+p=4; wherein R is a heterocyclic amine; wherein L is alinker group; and wherein R1 is a C1-C4 alkoxy, hydroxy, chloro, orC1-C4 ester group.
 25. The modified substrate of claim 24, comprisingthe structure

wherein, n≧2; L is a linker group; and wherein R is a heterocyclicamine.
 26. The modified substrate of claim 25, wherein R is one of atleast a hydantoin, imidazolidinone, oxazolidinone, isocyanurate,glycoluril, triazinedione, or piperidine.
 27. The modified substrate ofclaim 25, wherein R has the structure

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group.
 28. The modified substrate of claim 25, whereinR has the structure

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group.
 29. The modified substrate of claim 25, whereinR has the structure

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group.
 30. The modified substrate of claim25, wherein R has the structure

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group.
 31. The modified substrate of claim25, wherein R has the structure

wherein R4 is at least one of a C1-C4 alkyl, aryl, or hydroxymethylgroup.
 32. The modified substrate of claim 25, wherein R has thestructure

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group.
 33. The modified substrate of claim25, wherein R has the structure

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group; wherein X is independently selected fromhydrogen or hydroxymethyl, and wherein at least one X is hydrogen. 34.The modified substrate of claim 25, wherein R has the structure

wherein X is independently selected from hydrogen or hydroxymethyl, andwherein at least one X is hydrogen.
 35. The modified substrate of claim25, wherein R has the structure

wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl,or hydroxymethyl group; wherein X is independently selected fromhydrogen or hydroxymethyl, and wherein at least one X is hydrogen. 36.The modified substrate of claim 25, wherein R has the structure

wherein R4, R5, R6, and R7 are independently selected from a C1-C4alkyl, aryl, or hydroxymethyl group.
 37. A method for making a modifiedsubstrate, comprising: applying a compound of claim 1 and water to asubstrate; drying the substrate; and curing the substrate at atemperature sufficient to provide a modified substrate.